Vat dyestuffs of the 1.4.5.8-naphthoy-lene-diaryl-imidazol series and alpha process of preparing them



Patented Oct 3, 1933 TEs msm vA'rnYEsToFFsoF THE 1,;4n-m mox: 1

1 LBNEQDIARYL-IMIDAZOL simnis rnocnss or mummies-mm WIlheIm Eckei-t,Frankfort on Main-Boob, Germany, assignorto GeneralAniline Works,

Inc.,,1lew ascorporation' of Delav j No Application .14. 1929,.q; -cSerial No. 399,696, and in Germany October 29,

V 19 Claims. The present invention relates tovat dyestuffs oi e -l= -5-8r h hn ew =9 se i andtola process a: preparing them.

a I havefound that new vat dyestuffs of the naphth oylene diarylimidazol series are obtained by calming a naphthoylene-diaryl-imidazolcontaining halogen in the aryl groups'to react with nitrogenicontainingcompounds of the following eneral formula: RNH: wherein R-stands to!"asubstituted or unsubstituted aromatic group inca high boiling solventsuch as nitrobenzene,

naphthalene or v the like inthe presence of an acid-binding agents such,for; instance, as sodium acetate, potassium acetate, sodium carbonate,po- 3 tassium carbonate or thelike: The reaction mixture preferably isheated to the boiling point of the solvent and a catalyst such, forinstance, as metallic copper powder'or a copper salt such as cuprouschloride, copper chloride, copper acetate or the like may be added. I

The new vat dyestufisthus obtained have the following probable iormula:

. "z 7 wherein Z stands for thebivalent radical:

R representing a bivalent aromatic radical, .1

bound in o-positions to the nitrogen atoms and containing at least R1being a subsitlutedbr unsubstituted aromatic group. They have very goodfastness properties.

1 The naphthoylqene halogen diaryl -imidazols 1 I used asstartingfmaterials can, for instance, be prepared accordtngtotheprocessof U. S. patent specification No. 1,588,451, dated June 15,1926,

granted to Wilhelm Eckert and Heinrich Greune by condensing1A.5.8-naphthalene-tetra-carboxylicacid or the anhydride thereof withhalogen-ortho diamines, such toninstanoe, asichloroorbromo-ortho-phenylenediamine, or by direct iy halogenating thenaphthoylene-diaryl-imid one substituent of the group:fi

(01, 26644) i p p v Hereby; dyestufls are obtained, for instance, of thefollowingtype:

:?halogen.

L wherein .R represents the bivalent radical groups to react withorganichalogen com-- pounds. V v

The following examplesserve to illustrate my I invention but they .arenot intended t limit it thereto; the parts being by weight: g (1) 48parts of 1.4.5.8-naphthoylene-4.4'-

11 dichloro-dibenz-imidazol of the following probjable constitution: V,

I N. ,3 i

4 R-- i wherein 3. represents the bivalent radicalnaphthalene-tetracarboxylic.acid with 4-chlorophenyleriediamin;according to. the process of- (obtainable for intance by condensing1.4.5.8-

the above mentioned U. S. patent specification) are heated to boilingfor about 15'ho'ur's'to gether with parts of Mpha-amino-ahthra-F.

quinone in 1200 parts of nitrobenzenevwhile adding 20 parts of potassiumcarbonate and j-ljo parts j I 0f cuprous chloride. After cooling thereactionj product is filtered by suction, washed with alcohol,boilediout with water and dried; [Itfrepresentsa' nearly black powderdyeing cottonl from a greenish vat a very fastcorinth, whereas thestarting rnaterial dyes areddish brown shade, The product thus obtainedhas the following probable formula :1 I l t l wherein R. represents thebivalent radical The same dyestuffyisg obtained by causin 1 .415 .8.naphthoylene'-c4 .4? -diamino-,d=\ibenzimid' 'azol to' react in the same'wayiwithfan' alphachloroanthraquinone. The 1.4.5.8*-naphthoylene-=4.4"-diamino-dibenaiinidazolused as starting material may be obtained.for instance by con-Vv densing. 1.4.5;8-naphtha1ene tetra carboxylic Iacid with 4-nitr0-ortho-phenylene-diamine ac-..

cording to the processof the above mentioned U. S patentspecificationgand subsequently 'reducing the product thus obtained or bydirectly I nitrating and reducing the 1.4.5. 8-v-naphthoy1 y kdibenzimidazol, z

olffiimilal' properties-is ob- A dyestuff of equal tainedbycondensing asabove described with an alpha-aminoanthraquinone jthe' 'dyes'tulT' whichcan be prepared by brorninating the r 1.4.5.8-naphthoylene-dibenziniidazol in chloro sulfonic acid whileadding acatalystl (2) 57 parts of 1.4.5.8-naphthoylene-4.4" di-;bromo-dibenzimidazol of the following probable formula:

arid-52 parts or 1amino 5 benzoyl-amino anthralquinone are suspended in1'700pa'rts ofdrly' nitro' benzene. 20 parts of cuprous 1 chloride and20 parts of potassium carbonate areadded and the mixture isbolled foraboui'fz i hours. The dyestuff thus'obtainedis boiled'out-withchloroben- Ze'nefand washed with alcohol and water; It represents'a darkpowder which dissolves incon- (:fentrated sulfuric acid to a' brownsolution? It dyes cotton a dull bro'yvnshade. Its fastness propertiesare excellent. Itprobably has the following constitution:

' NE-"oo-mm wherein R represents t he bivalent radical I xi 7 Vs (3 'By;using instead .ofthe l-amino-S- benzoylaminoanthraquinoneof Example?equal parts oft .-1-amino l-benzoylamino-anthraquin one and proceedingin'the same manner as indi 1,928,710 v a 3 cated this example a dyestuffis obtained dyewhereinnremesents the bivalent. radicalmg'memsh-grey-tmts; ms difilcultly-soluble'in' w j 1 1 4 all, even inhot, organlc solvents and melts 1st 5 above 300C. It probably has thefollowing probv N s a Y able constitution: p 7 I v v C30 o)YNH;-C(I)CQH;'

' its"; 7

1 (5) 'parts of l.4.5.8-naphthoylene-4'Q4"-dl QC: C amino-dibenzimidazolof the following probable formula: V v

t 1 V V p N vN Whe 'eln R epresents the bivalent radical r oo o 9.

7' .tl i a LR; I

whereinR represents the bivalent radical ot i 0 j N N NH-CO-GQHs NH,

(4) A suspension 5'1 parts of 1.4.5.8-naphthoylene-4 .-4'-dibromo-dibenzimidazol, 20 parts of potassium acetate, 20 parts ofcuprous chloride (prepaz'ed by condensation- 0f1.4.5.8-naphthalene-tetracarboxylic acid with I4-nitro-L2-phenylene-diamine according to the process of the fi parts ofl-amino-zsmfihylanthmquinone above mentioned U. S. patent specificationand .2 u s in 1700 Parts Of ll i heated to boiling subsequent reduction){are-heated to boiling for 8 temperature. After about 24 hours thereaction hours inv 840 parts of benzoyl-ehloride. After is finished. Thehot condensation product is cooling the product thus formed is filteredby filtered by suotiumwashed with alcohol andboiled Suction andwashedwith alcohol. It represents with water. The dyestufi dissolves inconcena d -brown'powder whichdissolves in concentrated sulfuric acidandm concentrated hydrotrailed sulfuric a a brownish-red so chloric acidtoa brown solution. In organic sol- It dyes cotton X- l It vents it isinsoluble." It dyes cotton an intensive ablyrhas h followmgconstitutlon:

dull brown shade an probably has the following NHCO-Odzl; probableconstitutionzy V I a r n. R v a V N N u l: i H wherein R re resents thebivalentradical K v D (I) I v 14,5

' NH-CO-CuHu .150

(6) A suspension. of 11.4.5.8-naphthoylene 'Icl'aimz; 3 '-.5 -3 .5-tetra-brom.- dibenzimidazol following probable formula;

I V l Br of the wherein R represents the bivalent radical T Br i(prepared: by condensing the dianhydride of the 1L4.5.8naphthalenetetra-carboxylic acid or the said acid itself with 3.5 -dibr0mo-1;2diaminobenzene according. to the above mentioned U. S.

I patent specification), parts of alpha-aminoanthraquinone, 20 partsofanhydrous sodium acetate and 5 parts of copper acetate in 1200 partsofnitrobenzene is heated to boiling for l6-20 f hours. Aftercooling't'he-new'dyestufi'thus obtained is filtered by suction, washedwith alcohol and boiled with water.v It "represents a nearly blackpowder whioh dissolves in high-boiling hot organic solvents to a deepbrown solution; at a temperature of 300C. the dyestuif is not yetmolten. It dyes cotton ,from a clear brown vat greyish-brown tints andprobably has the following'constitutionze wherein Z stands for thebivalent radical: J

v (korinth) shadewith very good fastness'properties. V

.L- As new products the compounds of the-Iol-Q lowing probable formula:I t Y and Y for hydro gen or the group: -N'HR'1,HR1 being ananthraquinone group, at least one Y for the groupi-Nl-l-Rnwhich productsare almost black dyestufl's melting at above 300 C., dissolving inconcentrated sulfuric acid to a brown to brownish-red solution anddyeing cotton from the vat a bordeauX-red to deep brown (korinth) shadewith very good fastness properties.

2. As new products, the compounds of the following probable formu1a: 1

. 0= and- Y for hydrogen or theigroup:

l 7 X1 X1 wherein X1 standsgforfliydrogen or the group:

' -NH-acyl and Xz'for hydrogen or alkyl, at least one Y being the abovestated group, which products are almost black dyestufis melting at above300 0., dissolving in concentrated sulfuric acid to abrown tobrownish-redsolution and dyeing cotton from the vat abordeaux-red todeep brown m m gma the grgubjg I V r gmaavie;

lowing probable formula; o m

wherein X stands for hydrogen orthe group: a i -NH-CO.CaH5 and X: forhydrogen or methyl,

at least one Y being the above stated group, hich products are almostblack dyestuffs melting at above 300 C., dissolving'in' concentratedsulfuric acid to a brown to brownish-red solution and dye- 3 ing cottonfrom the vat a bordeauxred to' deep brown (Kori nth) shade with very,good 1a stness P operties, v V

4. As new products the compounds of the following probable formulaz Iwherein Z stands forthe bivalent radical:

.i V Y Y and a catalyst.- o

acid to a brown to brownish-red solution and dyeing cotton from the vata bordeaux-red to deep brown (korinth) shade with very good fastness'properties. o I V I 5. Theprocess of preparing vat dyestuffs whichvcomprises heating in a high boiling 'solventa1.4;5,8-naphthoylene-diaryl-imidazol the aryl of which; belongs to thebenzene series contains halogen with a compound of the general Iormulai'BhNHQ whereinR, stands for an aromatic carbo cyclic group in: thepresencelof an a'c'id-binding a ent; l,

at least one y being the above stated group, which products are almostblack dyestuifs melting at above 300 C., dissolving in concentratedsulfuric o- 6- e ro ssisr aanmla m comprises heating to boilingtemperature in a high-boiling solvent a 1.4.5.8-naphthoyle'ne-'diaryl-imidazol the 'aryl of whichbelongsto the 4, benzene series andcontains halogen with a j compound of the general. formula: R.NH2where-' I in R stands for an aromatic carbocycli'c group in the presenceof an acid-binding agent and a cata- 7. The processiof preparingvat'dyestufis which comprises heating in a high-boiling solvent a1.4.5.8-naphthoylene-dibenzimidazol containing 3 halogen in thebenzo-groups with a compound of the general formula: R.NH2 wherein Rstands foran aromatic carbocyclic group in thepresence of anacid-binding agent.

8. The process of preparing vat dyestuifs which comprises heatingtoboiling temperature'in a high-boiling solvent 9.1.4.5.8-naphthoylene-dibenzimidazol containingwhalogen in thebenzogroups with a compound or the general formula: R.NHz wherein Rstands-for an aromatic carbo cyclic group in the presence'of'an'acid-binding agent and a catalyst. V V. v QQfIhe process ofpreparing vat dyestuffs which comprises heating in a high-boilingsolvent a 1.4,5.8-naphthoylene-dibenzimidazol 1 containing halogen in;the benzo-groups with-a, compound of the generalformula: R,Nlh wherein Rstands for an anthraquinonyl groupin vthe presenceoi an acid-bindingagent. 7

10. The process of preparing vat dyestuffs which comprises heatingtoboiling temperature in a high-boiling solvent a 1'.4.5.8-naphthoylenedibenzimidazol containinghalogen in the benzo-'groups with a compound of the general formula:

;R.NH2 wherein. R stands for an anthroquinonyl group in-the presence ofan acid-binding agent t 11. The process ofop repiarin g a vat dyestufiwhich 'compriseshe'ating to boiling temperature for several hoursinnitrobenaene a 1.4.5l'8-naph thoylene-dibenzimidazol ot'the followingprobable formula; o

whereinR represents the bivalent radical I thoylene-dibenzimidazol ofthe .following probab1e ro ula'*t* which .compriseshea'ting to boilingtemperature for several hoursininitrobenzene a 1,4J.8-naphthoylene-dibenziniidazol "of the following probable formula:

II I TB- as a catalyst.

with the presence 1 it the benzene series bound in ortho-positions tothe nitrogen atoms and containing at least one substituent of .thegroupzgNHRl, R1 being an aromatic carbocyclic group which products aresw m" I newproductsythe'compounds of the followingprobable formular- R Iw? o I I f R wherein 2 stands for the bivalent radical I R Rrepresenting a bivalent aromatic radical of almost black dyestuifsmelting at above 300 C.,

' dissolving in concentrated sulfuric acid to a brown to brownish-redsolution and dyeing cotton from the vat a bordeanx-red to deep-brown(korinth) shade of very good fastness properties.

15. As new products, the compounds of the 11f] following probableformula:

wherein R represents the .bivalentradical I I I p I I 10 QB V- a V j twherein Z stands for the bivalent radical V with 1-amino5-benzoylaminoanthraquinone in Y thepresenceoi potassium carbonateandcupr'ous OJ I I chloride as a'catalyst. r N" i 45i 13. The process otprepari'ng a; vat dyestuff II R representing a phenylene radical boundin ortho-positions to'the nitrogen atoms and containing at least oncethe group -NHR1,'R1 being an aromatic carbocyclic group which productsare almost black dyestufis melting at above 300 C., dissolving inconcentrated sulfuric acid to a brown to brownish-red'solution anddyeing cotv I ton from the vat a bordeaux-red to deep brown (korinth)shade of very good fastness properties. 30' I 16. As new products, thecompounds of the following probable formula; I

I 00 I o wherein Z stands for the bivalent radical a 0 t v Rrepresenting a phenylene radical bound in ortho-positions to thenitrogen atoms and con- I at least once the group -'NHR1, R1 being ananthraquinone compound which products are almost black dyestuffs meltingat above 300 C.,

dissolving in concentrated sulfuric acid to a I brown tobrownish-redsolution and dyeing cotton from the vat a bordeaux-red todeep brown (korinth) shade of very good fastness properties. 17,. As anew product, the compound of the following'probable formula:

wherein R represents the bivalent radical said product being a nearlyblack powder which dyes cotton from a greenish vat very fast korinthtints.

18. As a new product, the compound of the following probableformula:

OiHrCO-HN wherein R represents the bivalent radical said product being adark powder which dissolves in concentrated sulfuric acid to a brownsolution and dyescotton a dull brown fastness properties.

shade of very good 19. As a new product, the. compound of the followingprobable formula:

V o a NH o: 0

wherein R represents the bivalent radical:

'said product being v a nearly black powder. which dissolves inhigh-boiling hot organic'solvents to a deep brown solution, does noteven melt at 300 C.

a clear brown vat'greyishand dyes cotton from 1 brown tints.

